Iron oxides are regarded as promising anodes for both lithium-ion batteries (LIBs) and potassium-ion batteries (KIBs) due to their high theoretical capacity, abundant reserves, and low cost, but they are also facing great challenges due to the sluggish reaction kinetics, low electronic conductivity, huge volume change, and unstable electrode interphases. Moreover, iron oxides are normally prepared at high temperature, forming large particles because of Ostwald ripening, and exhibiting low electronic/ionic conductivity and unfavorable mechanical stability. To address those issues, herein, we have synthesized ultra-small Fe₃O₄ nanodots encapsulated in layered carbon nanosheets (Fe₃O₄@LCS), using the coordination interaction between catechol and Fe³⁺, demonstrating fast reaction kinetics, high capacity, and typical capacitive-controlled electrochemical behaviors. Such Fe₃O₄@LCS nanocomposites were derived from coordination compounds with layered structures via van der Waals's force. Fe₃O₄@LCS-500 (annealed at 500 °C) nanocomposites have displayed attractive features of ultra-small particle size (∼5 nm), high surface area, mesoporous and layered feature. When used as anodes, Fe₃O₄@LCS-500 nanocomposites delivered exceptional electrochemical performances of high reversible capacity, excellent cycle stability and rate performance for both LIBs and KIBs. Such exceptional performances are highly associated with features of Fe₃O₄@LCS-500 nanocomposites in shortening Li/K ion diffusion length, fast reaction kinetics, high electronic/ionic conductivity, and robust electrode interphase stability.